AU702065B2

AU702065B2 - Curable coating composition including compound having carbamate and hydroxyl functionality

Info

Publication number: AU702065B2
Application number: AU68044/96A
Authority: AU
Inventors: Brian D. Bammel; John D. Mcgee; Gregory G Menovcik; Walter H Ohrbom; John W Rehfuss; Todd A Seaver
Original assignee: BASF Corp
Current assignee: BASF Corp
Priority date: 1995-10-06
Filing date: 1996-10-04
Publication date: 1999-02-11
Anticipated expiration: 2016-10-04
Also published as: MX215098B; DE69617156T2; JP3986595B2; KR970021226A; JPH09221633A; CA2187221A1; EP0767227B1; AU6804496A; ES2167501T3; DE69617156D1; MXPA96004596A; CA2187221C; CN1157843A; CN1102626C; US5792810A; EP0767227A1; BR9605013A; ATE209239T1

Abstract

A curable coating composition is described comprising (A) a compound comprising carbamate or urea and hydroxyl functional groups that is the reaction product of (1) a compound comprising a carbamate or urea group or a group that can be converted to a carbamate or urea group, and an active hydrogen group that is reactive with a lactone or a hydroxy carboxylic acid, and (2) a lactone or a hydroxy carboxylic acid, (B) a compound comprising at least one group that is reactive with carbamate and at least one group that is reactive with hydroxyl, or a plurality of groups that are reactive with both carbamate and hydroxyl.

Description

L e 2 4 -1- P/00/011 Regulation 3.2

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Invention Title: CURABLE COATING COMPOSITION INCLUDING COMPOUND HAVING CARBAMATE AND HYDROXYL FUNCTIONALITY I i

E

iii ,3 *r rr r*u u r The following statement is a full description of this invention, including the best method of performing it known to us: (J~a~F o

I

r s r r ~s 1*

I*C

i i r GH REF: P19343-BM:DAA:RK I~ 1 1A- CURABLE COATING COMPOSITION INCLUDING COMPOUND HAVING CARBAMATE AND HYDROXYL FUNCTIONALITY Field of the Invention This invention relates to curable coating compositions, particularly to curable compositions i utilizing a carbamate- or urea-functional compound as one of the components of the composition.

Background of the Invention Curable coating compositions such as thermoset coatings are widely used in the coatings art. They are often used for topcoats in the automotive and i industrial coatings industry. Color-plus-clear composite coatings are particularly useful as topcoats where exceptional gloss, depth of color, distinctness 15 of image, or special metallic effects are desired, The automotive industry has made extensive use of these i coatings for automotive body panels. Color-plus-clear composite coatings, however, require an extremely high degree of clarity in the clearcoat to achieve the desired visual effect. High-gloss coatings also eo*w.. require a low degree of -visual aberrations at the surface of the coating in order to achieve the desired visual effect such as high distinctness of image (DOI).

Such coatings are especially susceptible to a 25 phenomenon known as environmental etch. Environmental etch manifests itself as spots or marks on or in the finish of the coating that often cannot be rubbed out. i i

_I

I 4 -2 Curable coating compositions based on curable components having carbamate or urea functionality have been proposed in the art to provide etch-resistant coatings, U.S. Patent 5,356,669 and WO 94/10211.

In addition to resistance to environmental etch, a number of other characteristics can be desirable. For example, it may be desirable to provide a coating having a high degree of flexibility. This can be particularly advantageous if the substrate on which the coating is placed is itself flexible, as in the case of plastic, leather, or textile substrates.

It is also desirable to reduce the amount of solvent required in coating compositions in order to reduce the volatile organic content (VOC), which is better for the environment.

Finally, it is desirable to provide options of different types of carbamate- or urea-functional materials to provide coatings with a good combination of properties such as durability, hardness, and resistance to scratching, marring, solvents, and acids.

Summary of the Invention According to the present invention, there is provided a coating composition comprising a compound comprising carbamate or urea and hydroxyl functional groups that is the reaction product of a compound comprising a carbamate or urea group or a group that can be converted to a carbamate *or urea group, and an active hydrogen group that is 30 reactive with and a lactone or a hydroxy carboxylic acid, a compound comprising at least one group that is reactive with carbamate and at least one group that is reactive with hydroxyl, or a plurality of groups that are reactive with both carbamate and hydroxyl.

The present invention provides coatings having a good combination of properties such as ll ?I*YIULRi lyy_~_pL1;ZSi ~y Pi~- Yh(BLL~L~ marring, solvents, and acids. Coating compositions according to the invention can also provide low VOC levels, and can be used to prepare coatings having good flexibility for use over flexible substrates.

Description of the Preferred Embodiments According to the present invention, compound has carbamate or urea functionality and hydroxyl functionality, and is the reaction product of the compound having at least one carbamate or urea group (or a group that can be converted to carbamate or urea) and an active hydrogen group with the lactone or hydroxy carboxylic acid Carbamate groups can generally be characterized by the formula e g

C

0

II

-O----C-NHR

wherein R is H or alkyl, preferably of 1 to 4 carbon atoms. Preferably, R is H or methyl, and more preferably R is H. Urea groups can generally be characterized by the formula 0

NR'-C--NHR"

wherein R' and R" each independently represents H or alkyl, preferably of 1 to 4 carbon atoms, or R' and R" may together form a heterocyclic ring structure where R' and R" form an ethylene bridge).

The compound can be formed by reacting a lactone or hydroxy carboxylic acid with a compound having an active hydrogen group capable of undergoing a condensation reaction with the acid group of the hydroxy carboxylic acid or ring-opening the lactone hydroxyl, primary amine, acid) and a carbamate or urea group or a group that can be converted to carbamate or urea. When a compound having an active hydrogen group and a group that can be converted to II 4 carbamate or urea is used to react with the lactone or hydroxy carboxylic acid, conversion of the group to a carbamate or urea can be accomplished during or after the ring-opening reaction.

Compounds having a carbamate or urea group and an active hydrogen group are known in the art.

Hydroxypropyl carbamate and hydroxyethyl ethylene urea, for example, are well known and commercially available.

Amino carbamates are described in U.S. Patent 2,842,523. Hydroxyl ureas may also be prepared by reacting an oxazolidone with ammonia or a primary amine or by reacting ethylene oxide with ammonia to form an amino alcohol and then reacting the amine group of that compound or any other amino alcohol with hydrochloric acid, then urea to form a hydroxy urea. Amino ureas can be prepared, for example, by reacting a ketone with a diamine having one amine group protected from reaction by steric hindrance), followed by reaction with HNCO the product of the thermal decomposition of urea), and then water. Alternatively, these compouads can be prepared by starting with a compound having an active hydrogen and a group that can be converted to carbamate or urea as described below, and then converting that group to' the carbamate or urea prior to commencement of the reaction with the lactone or hydroxy carboxylic acid.

Groups that can be converted to carbamate include cyclic carbonate groups, epoxy groups, and unsaturated bonds. Cyclic carbonate groups can be converted to carbamate groups by reaction with ammonia or a primary amine, which ring-opens the cyclic carbonate to form a A-hydroxy carbamate. Epoxy groups can be converted to carbamate groups by first i converting to a cyclic carbonate group by reaction with

CO

2 This can be done at any pressure from atmospheric up to supercritical CO 2 pressures, but is preferably S under elevated pressure 60-150 psi). The I I temperature for this reaction is preferably 60-150 0

C.

Useful catalysts include any that activate an oxirane ring, such as tertiary amine or quaternary salts tetramethyl ammonium bromide), combinations of complex organotin halides and alkyl phosphonium halides

(CH

3 3 SnI, Bu 4 SnI, Bu 4 PI, and (CH 3 4 PI), potassium salts K 2 CO3,KI) preferably in combination with crown ethers, tin octoate, calcium octoate, and the like. The cyclic carbonate group can then be converted to a carbamate group as described above. Any unsaturated bond can be converted to carbamate groups by first reacting with peroxide to convert to an epoxy group, then with CO2 to form a cyclic carbonate, and then with ammonia or a primary amine to form the carbamate.

Other groups, such as hydroxyl groups or isocyanate groups can also be converted to carbamate groups to form a compound However, if such groups were to be present on the compound and then converted to carbamate after the reacting with the lactone or hydroxy carboxylic acid, they would have to be blocked so that they would not react with the lactone, the hydroxy carboxylic acid, or with the active hydrogen groups. When blocking these groups is not feasible, the conversion to carbamate or urea would have to be completed prior to reaction with the lactone or hydroxy carboxylic acid. Hydroxyl groups can be converted to carbamate groups by reaction with a monoisocyanate methyl isocyanate) to form a .a 30 secondary carbamate group or with cyanic acid (which may be formed in situ by thermal decomposition of urea) to form a primary carbamate group unsubstituted carbamates). This reaction preferably occurs in the presence of a catalyst as is known in the art. A hydroxyl group can also be reacted with phosgene and then ammonia to form a compound having primary carbamate group(s), or by reaction of a hydroxyl with ttaai 6 phosgene and then a primary amine to form a compound having secondary carbamate groups. Another approach is to react an isocyanate with a compound such as hydroxyalkyl carbamate to form a carbamate-capped isocyanate derivative. For example, one isocyanate group on toluene diisocyanate can be reacted with hydroxypropyl carbamate, followed by reaction of the other isocyanate group with an excess of polyol to form a hydroxy carbamate. Finally, carbamates can be prepared by a transesterification approach where hydroxyl group reacted with an alkyl carbamate methyl carbamate, ethyl carbamate, butyl carbamate) to form a primary carbamate group-containing compound.

This reaction is performed under heat, preferably in the presence of a catalyst such as an organometallic catalyst dibutyltin dilaurate). Other techniques for preparing carbamates are also known in the art and are described, for example, in P. Adams F. Baron, "Esters of Carbamic Acid", Chemical Review, 20 v. 65, 1965.

Groups such as oxazolidone can also be converted to urea after reaction with the lactone or hydroxy carboxylic acid. For example, hydroxyethyl oxazolidone can be used to react with the lactone or hydroxy carboxylic acid, followed by reaction of ammonia or a primary amine with the oxazolidone to generate the urea functional group.

Other groups, such as amino groups or isocyanate groups can also be converted to urea groups 30 to form a compound However, if such groups were to be present on the compound and then converted to urea after reaction with the lactone or hydroxy carboxylic acid, they would have to be blocked so that they would not react with the lactone, the hydroxy carboxylic acid, or with the active hydrogen groups. When blocking these groups is not feasible, the conversion to carbamate or urea would have to be meat a a.

a.

S. S

C

a...1 *a e.

teem .me.

a .a 'r i j 1 I L: L 1_11 Si 7 completed prior to the reaction with the lactone or hydroxy carboxylic acid. Amino groups can be converted to urea groups by reaction with a monoisocyanate methyl isocyanate) to form a secondary urea group or with cyanic acid (which may be formed in situ by thermal decomposition of urea) to form a primary urea group. This reaction preferably occurs in the presence of a catalyst as is known in the art. An amino group can also be reacted with phosgene and then ammonia to form a compound having primary urea group(s), or by reaction of an amino group with phosgene and then a primary amine to form a compound having secondary urea groups. Another approach is to react an isocyanate with a hydroxy urea compound to form a urea-capped isocyanate derivative. For example, one isocyanate group on toluene diisocyanate can be reacted with hydroxyethyl ethylene urea, followed by reaction of the other isocyanate group with an excess of polyol to form a hydroxy carbamate.

One preferred class of compounds having an active hydrogen group and a group that can be converted to carbamate is the hydroxyalkyl cyclic carbonates.

~Hydroxyalkyl cyclic carbonates can be prepared by a number of approaches. Certain hydroxyalkyl cyclic carbonates like 3-hydroxypropyl carbonate glycerine carbonate) are commercially available.

Cyclic carbonate compounds can be synthesized by any of several different approaches. One approach involves reacting an epoxy group-containing compound with CO 2 30 under conditions and with catalysts as described hereinabove. Epoxides can also be reacted with butyrolactone in the presence of such catalysts. In too another approach, a glycol like glycerine is reacted at temperatures of at least 80*C. with diethyl carbonate in the presence of a catalyst potassium carbonate) to form a hydroxyalkyl carbonate.

Alternatively, a functional compound containing a ketal j dl II II 8 of a 1,2-diol having the structure: x 0 o

R

can be ring-opened with water, preferably with a trace amount of acid, to form a 1,2-glycol, which is then further reacted with diethyl carbonate to form the cyclic carbonate.

-Cyclic carbonates typically have 5-6-membered rings, as is known in the art. Five-membered rings are preferred, due to their ease of synthesis and greater degree of commercial availability. Six-membered rings can be synthesized by reacting phosgene with 1,3propane diol under conditions known in the art for the formation of cyclic carbonates. Preferred hydroxyalkyl cyclic carbonates used in the practice can be represented by the formula: 20 20 i 0 0 .(R)n where R (or each instance of R if n is more than 1) is a hydroxyalkyl group of 1-18 carbon atoms, preferably 1-6 carbon atoms, and more preferably 1-3 carbon atoms, which may be linear or branched and may have subsituents in addition to the hydroxyl (which itself may be primary, secondary, or tertiary), and n is 1 or 2, which may be substituted by one or more other substituents such as blocked amines or unsaturated groups. More preferably, R is -Cm 2mOH where the i hydroxyl may be primary or secondary and m is 1 to 8, C1I -9 and even more preferably, R is -(CH 2 )p-OH where the hydroxyl is primary and p is 1 to 2.

Lactones that can be ring opened by an active hydrogen are well-known in the art. They include, for example, E-caprolactone, 7-caprolactone, 3butyrolactone, A-propriolactone, y-butyrolactone, amethyl-y-butyrolactone, g-methyl-y-butyrolactone, 7valerolactone, 6-valerolactone, 7-nonanoic lactone, 7octanoic lactone, and pentolactone. In one preferred embodiment, the lactone is E-caprolactone. Lactones useful in the practice of the invention can also be characterized by the formula: R O 0 wherein n is a positive integer of 1 to 7 and R is one or more H atoms, or substituted or unsubstituted alkyl groups of 1-7 carbon atoms.

The lactone ring-opening reaction is 20 typically conducted under elevated temperature 80-150 0 The reactants are usually liquids so a solvent is not necessary. However, a solvent may be useful in promoting good conditions for the reaction even if the reactants are liquid. Any non-reactive solvent may be used, including both polar and nonpolar organic solvents. Examples of useful solvents include ."04 toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and the like. A catalyst is preferably present. Usefsil catalysts include proton acids 30 octanoic acid, Amberlyst® 15 (Rohm Haas)), and tin catalysts stannous octoate). Alternatively, the reaction can be initiated by forming a sodium salt of the hydroxyl group on the molecules to react with the lactone ring.

i h~, 9 and even more preferably, R is -(CH 2 )p-OH where the hydroxyl is primary and p is 1 to 2.

Lactones that can be ring opened by an active hydrogen are well-known in the art. They include, for example, e-caprolactone, y-caprolactone, 8butyrolactone, /-propriolactone, y-butyrolactone, amethyl-y-butyrolactone, A-methyl-y-butyrolactone, 7valerolactone, 6-valerolactone, 7-nonanoic lactone, 7octanoic lactone, and pentolactone. In one preferred embodiment, the lactone is e-caprolactone. Lactones useful in the practice of the invention can also be characterized by the formula: R O 0 wherein n is a positive integer of 1 to 7 and R is one or more H atoms, or substituted or unsubstituted alkyl groups of 1-7 carbon atoms.

The lactone ring-opening reaction is typically conducted under elevated temperature 80-150°C.). The reactants are usually liquids so a solvent is not necessary. However, a solvent may be useful in promoting good conditions for the reaction even if the reactants are liquid. Any non-reactive solvent may be used, including both polar and nonpolar organic solvents. Examples of useful solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and the like. A catalyst is preferably present. Useful catalysts include proton acids 30 octanoic acid, Amberlyst® 15 (Rohm Haas)), and tin catalysts stannous octoate). Alternatively, the reaction can be initiated by forming a sodium salt of the hydroxyl group on the molecules to react with the lactone ring.

44e 4 .4 4es* 44,r 44 964 0 4 A. u '.444 4.44 /1 1 ~II. I i~lr -trP--.I~LP 1IQI*PBBsS~ C- The lactone ring-opening reaction provides chain extension of the molecule if sufficient amounts of the lactone are present. The relative amounts of the carbamate or urea compound and the lactone can be varied to control the degree of chain extension. The opening of the lactone ring with a hydroxyl or amine group results in the formation of an ester or amide and an OH group. The OH group can then react with another available lactone ring, thus resulting in chain extension. The reaction is thus controlled by the proportion of lactone in the relative te the amount of initiator compound In the practice of the present invention, the ratio of equivalents of lactone from to equivalents of active hydrogen groups on is preferably from 0.1:1 to 10:1, and more preferably from 1:1 to 5:1.

When the lactone is opened with an acid, the resulting compound has an acid group, which can then be converted to a hydroxyl group by well-known techniques such as reaction with ethylene oxide.

A compound having a hydroxyl active hydrogen group can also be reacted with a hydroxy carboxylic acid to form the carbamate- or ureafunctional compound Useful hydroxy carboxylic 25 acids include dimethylhydroxypropionic acid, hydroxy stearic acid, tartaric acid, lactic acid, 2hydroxyethyl benzoic acid, and N-(2hydroxyethyl)ethylene diamine triacetic acid. The reaction can be conducted under typical transesterification conditions, temperatures from room temperature to 150 0 C. with transesterification catalysts such as calcium octoate, metal hydroxides KOH), Group I or II metals Na, Li), metal carbonates K 2

CO

3 which may be enhanced by use in combination with crown ethers, metal oxides dibutyltin oxide), metal alkoxides NaOCH 3 A1(OC 3

H

7 3 metal esters stannous octoate, j 11 calcium octoate, or protic acids H 2 S0 4 MgCO 3 or Ph 4 SbI. The reaction may also be conducted at room temperature with a polymer-supported catalyst such as (Rohm Haas) as described by R. Anand, Synthetic Communications, 24(19), 2743-47 (1994), the disclosure of which is incorporated herein by reference. The reaction is preferably performed with an excess of compound to minimize selfcondensation of the hydroxy carboxylic acid.

The composition of the invention is cured by a reaction of the carbamate- or urea-functional compound with a component that is a compound having a plurality of functional groups that are reactive with the carbamate or urea groups on component Such reactive groups include active methylol or methylalkoxy groups on aminoplast crosslinking agents or on other compounds such as phenol/formaldehyde adducts, siloxane or silane groups, and anhydride groups. Examples of compounds include melamine formaldehyde resin (including monomeric or polymeric melamine resin and partially or fully alkylated :oo melamine resin), urea resins methylol ureas such Tas urea formaldehyde resin, alkoxy ureas such as p butylated urea formaldehyde resin), N-methylol o* 25 acrylamide emulsions, isobutoxy methyl acrylamide emulsions, polyanhydrides polysuccinic anhydride), and siloxanes or silanes dimethyldimethoxy silane). Aminoplast resin such as melamine formaldehyde resin or urea formaldehyde resin are especially preferred. Also preferred are aminoplast resins where one or more of the amino nitrogens is substituted with a carbamate group for use in a process with a curing temperature below 150C., %s described in U.S. patent 5,300,328.

35 A solvent may optionally be utilized in the coating composition used in the practice of the present invention. The coating composition according to the 12 present invention can be applied without solvent, especially if the degree of chain extension for component is limited. However, in many cases, it is desirable to use a solvent in the coating composition as well. This solvent should act as a solvent with respect to both the carbamate- or ureafunctional compound as well as the component In general, depending on the solubility characteristics of components and the solvent can be any organic solvent and/or water. In one preferred embodiment, the solvent is a polar organic solvent.

More preferably, the solvent is a polar aliphatic solvent or polar aromatic solvents. Still more preferably, the solvent is a ketone, ester, acetate, aprotic amide, aprotic sulfoxide, or aprotic amine.

Examples of useful solvents include miethyl ethyl ketone, methyl isobutyl ketone, amyl acetate, ethylene glycol butyl ether-acetate, propylene glycol monomethyl ether acetate, xylene, N-methylpyrrolidone, or blends of aromatic hydrocarbons. In another embodiment, the solvent can be water or a mixture of water with co- •L solvents.

The coating composition used in the practice of the invention may include a catalyst to enhance the cure reaction. For example, when aminoplast compounds, especially monomeric melamines, are used as component a strong acid catalyst may be utilized to enhance .the cure reaction. Such catalysts are well-known in the art and include, for example, p-toluenesulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzenesulfonic acid, phenyl acid phosphate, monobutyl maleate, butyl phosphate, and hydroxy phosphate ester. Other catalysts that may be useful in the composition of the invention include Lewis acids, zinc salts, and tin salts.

Although a colvent may be present in the coating composition in an amount of 2rom about 0.01

L

13 weight percent to about 99 weight percent, it is preferably present in an amount of less than 30%, more preferably less than 20% and most preferably less than The coating composition preferably has a VOC (VOC is defined herein as VOC according to ASTM D3960) of less than 3.0 Ibs/gal, more.preferably less than Ibs/gal, and most preferably less than 1.0 ibs/gal.

Coating compositions can be coated on the article by any of a number of techniques well-known in the art. These include, for example, spray coating, dip coating, roll coating, curtain coating, and the like. For automotive body panels, spray coating is preferred. One advantage that can be achieved with coating compositions according to the invention is that coatings with a high degree of flexibility can be prepared. Accordingly, in a preferred embodiment, the substrate onto which the coating is applied is flexible, such as plastic, leather, or textile substrates. Any additional agent used, ior example, surfactants, fillers, stabilizers, wetting agents, r dispersing agents, adhesion promoters, UV absorbers, HALS, etc. may be incorporated into the coating composition. While the agents are well-known in the 9° 25 prior art, the amount used .must be controlled to avoid o" adversely affecting the coating characteristics.

In one preferred embodiment, the coating composition according to the invention is preferably utilized in a high-gloss coating and/or as the clearcoat of a composite color-plus-clear coating.

High-gloss coatings as used herein are coatings having a 200 gloss (ASTM D523-89) or a DOI (ASTM E430-91) of at least 80. In other preferred embodiments, the coating composition may be utilized to prepare high- 35 gloss or low-gloss primer or enamel coatings.

When the coating composition of the invention is used as a high-gloss pigmented paint coating, the i K ~s 14 J 14 pigment may be any organic or inorganic compounds or colored materials, fillers, metallic or other inorganic flake materials such as mica or aluminum flake, and other materials of kind that the art normally names as pigments. Pigments are usually used in the composition in an amount of 2% to 350%, based on the total weight (not including solvent) of components A and B a P:B ratio of 0.02 to When the coating composition according to the invention is used as the clearcoat of a composite color-plus-clear coating, the pigmented basecoat composition may be any of a number of types well-known in the art, and does not require explanation in detail herein. Polymers known in the art to be useful in basecoat compositions include acrylics, vinyls, polyurethanes, polycarbonates, polyesters, alkyds, and siloxanes. Preferred polymers include acrylics and polyurethanes. In one preferred embodiment of the invention, the basecoat composition also utilizes a carbamate-functional acrylic polymer. Basecoat polymers are preferably crosslinkable, and thus comprise one or more type of cross-linkable functional groups. Such groups include, for example, hydroxy, isocyanate, amine, epoxy, acrylate, vinyl, silane, and *25 acetoacetate groups. These groups may be masked or blocked in such a way so that they are unblocked and available for the cross-linking reaction under the S desired curing conditions, generally elevated temperatures. Useful cross-linkable functional groups ,nclude hydroxy, epoxy, acid, anhydride, silane, and acetoacetate groups. Preferred cross-linkable functional groups include hydroxy functional groups and amino functional groups.

Basecoat polymers may be self-cross-linkable, or may require a separate cross-linking agent that is reactive with the functional groups of the polymer. When the polymer comprises hydroxy functional groups, for example, the cross-linking agent may be an aminoplast resin, isocyanate and blocked isocyanates (including isocyanurates), and acid or anhydride functional cross-linking agents.

The coating compositions described herein are preferably subjected to conditions so as to cure the coating layers. Although various methods of curing may be used, heat-curing is preferred. Generally, heat curing is effected by exposing the coated article to elevated temperatures provided primarily by radiative heat sources. Curing temperatures will vary depending on the particular blocking groups used in the crosslinking agents, however they generally range between 93 0 C. and 177 0 C. The coating composition according to the present invention is curable even at relatively low cure temperatures. Thus, in a preferred embodiment, the cure temperature is preferably between 115 0 C. and 150 0 and more preferably at temperatures between 115 0 C. and 138 0 C. for a blocked acid catalyzed system.

For an unblocked acid catalyzed system, the cure temperature is preferably between 82 0 C. and 99 0 C. The curing time will vary depending on the particular components used, and physical parameters such as the thickness of the layers, however, typical curing times *0 0 25 range from 15 to 60 minutes, and preferably 15-25 minutes for blocked acid catalyzed systems and 10-20 minutes for unblocked acid catalyzed systems.

The invention is further described in the following examples.

Preparation 1 Compound (A) mit f A clean 5-liter three-necked round bottomed ieo flask was equipped with an agitator, condenser, thermocouple, and nitrogen'line. To this apparatus was i added 1735.0 g E-caprolactone, 761.9 g hydroxypropyl i 35. carbamate, 234 g xylene, and 4.4 g stannous octoate.

The mixture was stirred under nitrogen atmosphere and heated to a temperature of 130 0 C. Temperature was

L,

16 maintained for a period of 6 hours to complete the synthesis, and then cooled.

Example 1 Coating Composition A clearcoat composition was prepared by mixing 1000 g of Preparation 1, 337.4 g monomeric fully metholated melamine, and 6.1 g dodecylbenzyl sulfonic acid.

This composition was spray-applied to a variety of substrates using a conventional air atomization siphon gun. Both rigid and flexible substrates were coated. A portion of the pazl%.s were applied wet on wet over conventional high o.i'its basecoat. For these systems, the basecoat ,art industry standard high-solids OH acrylic/melamine system) was applied, followed by a 10-minute ambient flash, at which point the above-described coating composition was applied. After an additional 5 minutes ambient flash, the panels were baked at 250 0 F. for 30 minutes.

The coating composition of the Example resulted in a contiguous cured hard clear film. The measured VOC of the clearcoat mixture was found to be 1.2 Ibs/gal.

The invention has been described in detail with reference to preferred embodiments thereof. It should be understood, however, that variations and modifications can be made within the spirit and scope of the invention.

e* S 0oS S r j i

Claims

1. 17 The claims defining the invention are as follows: 1. A curable coating composition comprising a compound comprising carbamate or urea and hydroxyl functional groups that is the reaction product of a compound comprising a carbamate or urea group or a group that can be converted to a carbamate or urea group, and an active hydrogen group that is reactive with and a lactone or a hydroxy carboxylic acid, a compound comprising at least one group that is reactive with carbamate and at least one group that is reactive with hydroxyl, or a plurality of groups that are reactive with both carbamate and hydroxyl.

2. A coating composition according to claim 1, wherein the active hydrogen group on compound (1.3 is a hydroxyl group.

3. A coating composition accordixg o claim 1, wherein the active hydrogen group on compound is an amino group.

4. A coating composition according to claim 1, wherein said compound comprises carbamate and hydroxyl functional groups. A coating composition according to claim 1, wherein said compound comprises urea and hydroxyl functional groups.

6. A coating composition according to claim 1, wherein compound is a hydroxyalkyl carbamate or a hydroxyalkyl cyclic carbonate.

7. A coating composition according to claim 1, wherein compound is a #-hydroxy carbamate that is a product of a ring-opened cyclic carbonate.

8. A coating composition according to any of the preceding claims, wherein the compound is a lactone.

9. A coating composition according to claim 8, wherein the ratio of equivalents of lactone from to equivalents of active hydrogen groups on is from 0.1:1 to 10:1. A coating composition according to any of the iir a4 4 I .44. L 1 'a, ii it Ii i i: i- i i (i S18 preceding claims, wherein the ratio of equivalents of lactone from to equivalents of active hydrogen groups on is from 1:1 to 5:1.

11. A coating composition according to any of the preceding claims, wherein compound is an aminoplast.

12. A coating conpofition according to claim 11, wherein said aminoplast is a melamine resin.

13. A coating composition according to any of the preceding claims, having a VOC of less than 3.0 Ibs/gal.

14. A coating composition according to any of the preceding claims, having a VOC of less than 2.0 lbs/gal. A coating composition according to any of the preceding claims, having a VOC of less than 1.0 Ibs/gal.

16. A coating composition according to any of the preceding claims, that is a liquid and comprises less than weight percent of nonreactive organic solvent.

17. A coating composition according to claim 16, that is a liquid and comprises less than 20 weight percent of nonreactive organic solvent.

18. A coating composition according to claim 16, that is a liquid and comprises less than 10 weight percent of nonreactive organic solvent.

19. A coating composition according to any of the preceding claims, that is a clear coating composition. A coating composition according to any of the tI preceding claims, further comprising a pigment. S21. An article comprising a substrate having thereon a cured coating derived from a coating composition according to Sany of claims 1-20. *22. An article according to claim 21, wherein said substrate is a flexible substrate.

23. A coating composition substantially as hereinbefore described in any of the Examples. Dated this 4th day of October 1996 «6 BASF CORPORATION By their Patent Attorney GRIFFITH HACK -rr7 CURABLE COATING COMPOSITION INCLUDING COMPOUND HAVING CARBAMATE AND HYDROXYL FUNCTIONALITY ABSTRACT A curable coating composition is described comprising a compound comprising carbamate or urea and hydroxyl functional groups that is the reaction product of a compound comprising a carbamate or urea group or a group that can be converted to a carbamate or urea group, and an active hydrogen group that is reactive with a lactone or a hydroxy carboxylic acid, and a lactoe or a hydroxy carboxylic acid, a compound comprising at least one group that is reactive with carbamate and at least one group that is reactive with hydroxyl, or a plurality of groups that are reactive with both carbamate and hydroxyl. 9 .4 44, AL., 0#46 i: I 9 99J4